Derivatives of 3-arylazo-naphthalenesulfonic acid



DERIVATIVES OF B-ARYLAZO-NAPHTHALENE- SULFONIC ACID Takeo Ueda, Tsuneo Wachi, and Tomoo Ito, Tokyo-to, Japan, assignors to Dainippon Pharmaceutical Co., Ltd., HIgashi-ku, Osaka, Japan No Drawing. Application May 13, 1957 Serial No. 658,500

Claims priority, application Japan January 29, 1952 2 Claiins. (Cl. 260-196) This application is in part a continuation of copending application Serial No. 300,524, filed July 23, 1952, now abandoned.

The group of compounds embodying this invention correspond to the following formula --N=N-Z 1: wherein X is an -SOzNHO C on or an -SOzNH coon radical, Y is OH or NH and Z is phenyl, o-methylphenyl, p-methylphenyl, p-carboxyphenyl, p-carbamylphenyl, pcarbonamidophenyl and p-acetylphenyl.

The aforesaid compounds are useful for dyeing, in essentially conventional manner, a wide variety of materials, such as Wool, silk, etc., deep and uniformly level shades being obtained. Moreover, like Congo red (H. J. Murray et a1: Proceeding 'of Society of Experimental and Biological Medicine, vol. 72, page 275, 1949), the new azo dyestuifs are characterized by antiviral activity.

The following examples which aredirected by way of illustration to representative embodiments of the invention show how the compounds of the present invention'may be prepared. In these examples, the relationship of parts by weight to parts by volume is the same as that between grams and milliliters.

EXAMPLE 1.

3-(p-carb0xyph enylazo '4-amiri0naphthalenesulfonamide-(1) 1.35 parts by Weight of p-aminobenzoic acid dissolved in 25 parts by volume of water containing 2.5 parts by volume of concentrated hydrochloric acid and cooled externally with ice, was diazotized with a solution of 0.8 part by weight of sodium nitrite in 5 parts by volume of water. The solution of the diazoniurn vsalt was neutralized by means of sodium acetate, and mixed, with a mixture, the precipitate was "filtered and recrystallized United States Patent 0 1C6 Patented Mar. 10, 1959.

from ethanol to dark-red fine needles, melting with deweight.

Analysis for C H O N S: N (calculated), 15.68%; N (found), 15.55%.

EXAMPLE 2 o (3-phenylaz0 4 aminonaphthalenerulfonamido)-benzoic acid 0.46 part by weight of aniline dissolved in 10 parts by volume of water containing 1.3 parts by volume of concentrated hydrochloric acid and cooled externally with ice, was diazotized with a solution of 0.4 part by weightof sodium nitrite in 5 parts by volume of water. The solution of the diazonium salt was neutralized by means of sodium acetate, and mixed, with agitation, with a cooled solution of 1.7 parts by weight of o-(4-aminonaphthalenesulfonamide)-benzoic acid and 0.6 part by weight of sodium carbonate in 200 parts by volume of ethanol, and the mixture was allowed to stand overnight in an ice-box. After the ethanol was removed by evaptvration out of the reaction mixture, the precipitate was filtered and recrystallized from ethanol to orange line needles, melting with decomposition at ca. 240 C. The yield was 2.5 parts by weight.

Analysis for C i-1 0 14 8: N (calculated), 12.55%; N (found), 12.71%.

EXAMPLE 3 0-[3-(p carboxyphenylazo)-4-aminonaphthalenesulfonamido] -benzoic acid volume of pyridine, the temperature being kept below 5 C. After 2 hours stirring, 50 parts by volume of water was added to the reaction solution, and the mixture was then allowed to stand overnight. The precipitate thus obtained was filtered, and recrystallized from metha nol. The yield was 2.1 parts by weight. This substance was obtained as reddish orange fine needles, melting with decomposition at 276 C.-277 C. It'was insoluble in water, ether and benzene, and soluble in alcohol and aqueous caustic soda solution;

Analysis for C24H130 N4S: N (calculated), v N (found), 11.29%.

EXAMPLE 4 p-(3-phenylaz0-4-aminonaphthalenesulfonamido)- benzoic acid v I r 0.9 part by weight of aniline dissolved in a mixture of 20 parts by volume of water and 2.5 parts by volume of concentrated hydrochloric acid was diazotized with a solution of 0.8 part by weight of sodium nitrite in 5 3 product was 2.6 parts by weight. This-"substance was obtained as orange' fine needles, melting with decomposition at 266 C.267 C. It was insoluble in water and benzene, and soluble in ether, alcohol and aqueous causticv soda solution.

Analysis for c n omsr N' (calculated), 12.55%; N (found), 12.42%.

EXAMPLE 5 I p [3 (p carboxyphenylazo) 4 aminonaphthalenesulfonamidol-benzoic acid 0.65 part by weight of p-aminobenzoic acid dissolved in a mixture of 10 parts by volume of water and 1.3

parts by volume of concentrated hydrochloric acid was diazotized with a solution of0.4 part by weight of sodium nitrite in 5 parts by volume of water. The solution of the diazonium salt thus prepared was dropped, with stirring, into a solution of 1.7 parts by weight of'p-(4- amlnonaphthalenesulfonamide)-benzoic acid in a mixture of 200 parts by volume of methanol and 2 parts by volume of pyridine, the temperature being kept below 10 C. After 2 hours stirring, 200 parts by volume of water was added to the reaction solution, and the mix ture was allowed to stand overnight. The precipitate thus obtained was filtered, and recrystallized from a mixture of acetone, methanol and water. The yield of product was 1.3 parts by weight. This substance was obtained as reddish orange fine needles, melting with decomposition at ca. 303 C; It was insoluble in water, ether and benzene, and soluble in alcohol and: aqueous caustic soda solution.

Analysis for C H O N S: Nv (calculated), 11.42%; N (found), 11.35%.

EXAMPLES 3 (p carbamylphenylazo) 4 aminonaphthalenesulfonamia'e- 2.7 parts by. weight of, p-aminobenzamide dissolved in a mixture of 20 parts by volume of water and 5' parts by volume of concentrated hydrochloric acid was diazotized with a solution of 1.5 parts by weight of sodium nitrite in 5 parts by volume of water. The solution of the diazonium salt thus prepared was. dropped, with stirring, into a solution of 4.5 parts by weight of 4-aminonaphthalenesulfonamide in a mixture of 400 parts by volume of methanol, 50 parts by volume of water and 8 parts by volume of pyridine, the temperature being kept below 10 C. After 2 hours stirring, 100 parts by volume .of water was added to the reaction mixture, and themixture was allowed to stand overnight. The precipitate thus obtained was filtered, and recrystallized from.60% alcohol. The yield was 3.5 parts by weight. This substance was red fine needles, and melted. at 244 C.-245 C. It was insoluble in water, ether and benzene, but soluble in either alcohol or aqueous caustic soda solution.

Analysis for C17H15O3N5S: N (calculated), 18.97%; N (found), 18.86%.

EXAMPLE 7 3 (p carboxyphenylazo) 4 hydroxynaphthalenesulfonic acid-(1) 1.4 parts by weight of p-aminobenzoic acid were dis solved in 10 parts by volume of water containing 2 parts by, volume of 38% hydrochloric acid, and diazotized by 1 part by volume of 30% sodium nitrite solution at' a temperature of C.--' C; This diazotized solution Recrystallization was effected Analysis for C H O N S: N (calculated), 7.52%; N (found), 7;43%.

EXAMPLE 8 3 (0 carboxyphenylazo) 4. hydroxynaphthalenesulfonic' acid (1) 2.2 parts by weight of. wnaphtholsulfonic acid-(4) and 1.4 parts by weight'of' o-aminobenzoic acid were treated according tov the method as in Example 7, and redneedles were obtained, in. 3.1 parts. by weightyield.

Analysis for C H O N S: N (calculated), 7.52%; N (found), 7.55%.

EXAMPLE 9 3 (p carbonamidophenylazo) 4 hydroxynaphthalenesulfom'c acid-(1) 2.2 parts by weight of a-naphtholsulfonic acid-(4) and 1.4 parts by weight of p-aminobenzamide were treated according to the method as in- Example 7, and. red needles were obtained. The yield was 3 parts by weight.

Analysis for C H O N S: N (calculated), 11.31%; N (found), 11.56%.

EXAMPLE 10 3-(p-carboxyphenylazo)-4-hydroxynaphthalenesulfonamide-(I 0.27 part by weight of p-aminobenzoic acid was diazotized after the manner described in Example 7, and was then neutralized by the addition of sodium acetate. The resultant solution was mixed with 0.45 part by weight of 4-hydroxynaphthaleuesulfonamidee(1) dissolved in 2.5 parts by volume of 5% caustic soda solution and 10 parts by volumeof water. The resulting red precipitate The precipitate was recryswas isolated by filtration.

The yield tallized from methanol yielding red needles. was 0.3 part by weight. t

Analysis for C I-I O NS: N (calculated), 11.31%; N (found), 11.47%.

EXAMPLE 11 3- (p-carboxyphenylazo) -4-hydroxynaph thal'en esulfonamid'e EXAMPLE 12 p-[ (3-p-carbamylphenylazo)-4-aminonaphzhalene- .suljomzmido]-benz0ic acid 0.65 part by weight of p-aminobenzamide dissolved in 10. parts by volume of water containing 1.3 parts by volume of concentrated hydrochloric acid, was diazotized with a solution of 0.4 part by weight of sodium nitrite in 5 parts by'vclume of water. This solution of the diazoniumsalt was. dropped, with stirring, into a solution: of 1.7 parts; by weight of'p-(4aaminonaphthalenesnlfonamido)"-benzoic acid in a mixture of 200-parts- .by'volume of methanol and 2v parts'by'volume of pyriadine, the: temperature being kept below. 10 C. After- 2 hours stirring, parts by volume of water was-I added to the reaction, mixture, and. the mixture was The; precipitate?- thus: obtained was: filtered, and; recrystallized. from: a mixture ofacetone, alcohol. and-water. Theyield. was: 1.2; parts.

allowed; to stand overnight.

by weight. This product was obtained as reddish orange fine needles melting with decomposition at 271 C.-272 C. It was insoluble in water, ether and benzene, and soluble in alcohol and aqueous caustic soda solution.

Analysis for C H O N S: N (calculated), 14.32%; N (found), 14.22%.

EXAlVIPLE 13 [3- (p-carbamylphenylazo) -4-aminonaphthalenesulfonamidel-benzoic acid 1.3 parts by weight or" p-aminobenzarnide dissolved in 20 parts by volume of water containing 2.5 parts by volume of concentrated hydrochloric acid, was diazotized with a solution of 0.8 part by Weight of sodium nitrite in 5 parts by volume of Water. The solution of the diazonium salt thus prepared was dropped, with stirring, into a solution of 3.4 parts by weight of o-(4-aminonaphthalenesulfonamido)-benzoic acid in a mixture of 260 parts by volume of methanol, 30 parts by volume of water and 4 parts by volume of pyridine, the temperature being kept below C. After 3 hours stirring, 100 parts by volume of water was added to the reaction mixture, and the mixture thus obtained was allowed to stand overnight. The precipitate thus obtained was filtered, and recrystallized from a mixture of acetone, alco- 1101 and water. The yield was 2.9 parts by weight. This substance was obtained as reddish-orange fine needles, melting with decomposition at 261 C.-262 C. It was insoluble in water, ether and benzene, and soluble in either alcohol or caustic soda solution.

Analysis for C H 0 N S: N (calculated), 14.32%; N (found), 14.02%.

EXAMPLE 14 p-(3-phenylazo-4-hydr0xynaphthalenesulfonamido)- benzoic acid 0.5 part by weight of p-(4-hydroxynaphthalenesulfonamido)-benzoic acid was dissolved in 20 parts by volume of methanol containing 1 part by volume of pyridine, and to this solution was added a solution which was prepared by diazotizing 0.14 part by weight of aniline with 0.13 part by weight of sodium nitrite. The reaction mixture thus prepared was allowed to stand for 2 hours, and the resulting precipitate was filtered out, and recrystallized from methanol to yield red needles which melted at 281 C. with decomposition. The yield of product was 0.47 part by weight.

Analysis for C23H17O5N3S: N (calculated), 9.39%; N (found), 9.31%.

EXAMPLE 15 o-(3-phenylazo-4-hydroxynaphthalenesulfonamido)- benzoic acid 1.5 parts by weight of o-(4-hydroxynaphthalenesulfonamido)-benzoic acid and 0.5 part by weight of aniline were treated according to the method as in Example 14, and there were obtained red needle crystals, which melted at 254 C. with decomposition. The yield was 1.3 parts by weight.

Analysis for C H O N S: N (calculated), 9.39%; N (found), 9.10%.

EXAMPLE 16 p-[S-(p-methylphenylazo) -4-hydroxynaphthalenesuljonamia'o] -benzoic acid 0.31 part by weight of p-(4-hydroxynaphthalenesulfonamido)-benzoie acid was dissolved in 30 parts by volume of methanol containing 1 part by volume of pyridine, and to this solution was added a solution which was prepared by diazotization of 0.1 part by weight of p-toluidine. The reaction mixture thus prepared was allowed to stand overnight, and the resulting precipitate was isolated by filtration, and recrystallized from methanol to yield red needles which melted at 276 C. with decomposition. The yield was 0.29 part by weight.

Analysis for C H O N S: N (calculated), 9.11%; N (found), 9.38%.

EXAMPLE 17 X wherein X is a member selected from the class consisting of -s omn-O-oo on SOaN'H JOOE radicals, Y is a member selected from the group consisting of OH and NH and Z is a member selected from the group consisting of the phenyl, o-methylphenyl, pmethylphenyl, p-carboxyphenyl, p-carbamylphenyl, p-carbonamidophenyl and p-acetylphenyl.

2. p (3-phenylazo-4-aminonaphthalenesulfonamido)- benzoic acid.

and

References Cited in the file of this patent UNITED STATES PATENTS 333,041 Vollbrecht et al. Dec. 22, 1885 498,982 Krekeler et al. June 6, 1893 2,302,955 Raiziss et al Nov. 24, 1942 2,340,584 Dohrn et a1. Feb. 1, 1944 2,434,173 Mackenzie et al. Jan. 6, 1948 2,498,418 Hanford Feb. 21, 1950 FOREIGN PATENTS 2,237 Great Britain of 1883 5,515 Great Britain of 1883 86,314 Germany Mar. 27, 1896 OTHER REFERENCES Conant: I. A. C. 8., vol. 48, 1926, pages 2476-7. 

1. A COMPOUND OF THE FORMULA 